基于原位电化学石英晶体微天平技术的硅基负极粘结剂性能分析

引用本文: 崔亚楠, 孙琪, 任晓燕, 逯乐慧. 基于原位电化学石英晶体微天平技术的硅基负极粘结剂性能分析[J]. 分析化学, 2022, 50(3): 384-391. doi: 10.19756/j.issn.0253-3820.210874 shu

Citation: CUI Ya-Nan, SUN Qi, REN Xiao-Yan, LU Le-Hui. Performance Analysis of Binders for Silicon Anodes by In-situ Electrochemical Quartz Crystal Microbalance Technique[J]. Chinese Journal of Analytical Chemistry, 2022, 50(3): 384-391. doi: 10.19756/j.issn.0253-3820.210874 shu

基于原位电化学石英晶体微天平技术的硅基负极粘结剂性能分析

崔亚楠 ^1,2, ,
孙琪 ^1,2, ,
任晓燕 ^{1,
,} ,
逯乐慧 ^{1,2,
,}

¹中国科学院长春应用化学研究所电分析化学国家重点实验室, 长春 130022;
²中国科学技术大学应用化学与工程学院, 合肥 230026

通讯作者: 任晓燕,E-mail:xyren@ciac.ac.cn; 逯乐慧,E-mail:lehuilu@ciac.ac.cn

基金项目:
国家自然科学基金项目（Nos.21874127，22004115，21721003）资助。

摘要: 粘结剂是锂离子电池硅基负极材料的重要组成部分，与锂离子电池的性能密切相关。本研究选取两类不同作用机制的典型粘结剂聚偏二氟乙烯（PVDF）和海藻酸钠（ALG），通过原位与非原位结合的方式对不同作用机制的粘结剂对硅电极充放电过程电化学行为的影响进行了初步探讨。首先利用恒电流充放电测试、循环伏安法、交流阻抗法和扫描电子显微镜等方法对粘结剂的粘结效果进行表征和评估。结果表明，使用ALG作为粘结剂的硅电极可以稳定循环200圈，每圈循环容量衰减率仅为0.2%，并且电极表面平整，电化学阻抗小，与使用PVDF作为粘结剂的硅电极相比优势明显。为了深入分析造成差异性结果的原因，引入原位电化学石英晶体微天平技术（In-situ electrochemical quartz crystal microbalance，In-situ EQCM）实时、定量地记录首圈放电时硅基负极表面的质量和电流变化过程。结果表明，粘结剂ALG的羧基基团与硅表面羟基基团间的氢键相互作用增强了纳米硅颗粒对集流体的黏附作用，促进电极表面生成薄而致密的固体电解质界面（SEI）膜，并且减少了电极表面电解液的分解，从而显著提高了电化学性能。

关键词:

English

Performance Analysis of Binders for Silicon Anodes by In-situ Electrochemical Quartz Crystal Microbalance Technique

CUI Ya-Nan ^1,2, ,
SUN Qi ^1,2, ,
REN Xiao-Yan ^{1,
,} ,
LU Le-Hui ^{1,2,
,}

¹State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;
²School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China

Corresponding author: REN Xiao-Yan, ; LU Le-Hui,

Received Date: 02 December 2021
Revised Date: 13 January 2022
Fund Project:
Supported by the National Natural Science Foundation of China (Nos.21874127, 22004115, 21721003).

Abstract: Binders play an important role in the commercialization of silicon anodes. Herein, two kinds of commonly used commercial binders, polyvinylidene difluoride (PVDF) and sodium alginate (ALG), were characterized with cyclic charge-discharge test, cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy. The results showed that silicon electrode using binder ALG endowed enhanced cycling stability (200 cycles at 0.1 C) and low-capacity fading rate (0.2% per cycle). In comparison with silicon electrode using binder PVDF, the surface of silicon electrode using ALG was much smoother and exhibited lower impedance after cycling. Furthermore, in-situ electrochemical quartz crystal microbalance (In-situ EQCM) was then introduced to quantitatively record the quality and current changes of electrode in real time, and the generation process of solid electrolyte interface (SEI) film was further analyzed. The analysis results showed that the hydrogen bond interaction between the carboxyl group of binder ALG and the hydroxyl group on silicon electrode could enhance the adhesion of nano-silicon particles to the current collector, promote the formation of a thin and dense SEI film on the electrode surface, reduce the decomposition of electrolyte, and significantly improve the electrochemical performance. In this study, a combination of in-situ and ex-situ characterization was used to make a preliminary discussion on the mechanism of different binders during the charge and discharge process of silicon electrodes.

Key words:

Sodium alginate
/ Polyvinylidene difluoride
/ Silicon anodes
/ Binder
/ In-situ electrochemical quartz crystal microbalance

1. [1]
  OBROVAC M N, CHEVRIER V L. Chem. Rev., 2014, 114(23):11444-11502.OBROVAC M N, CHEVRIER V L. Chem. Rev., 2014, 114(23):11444-11502.
2. [2]
  TRIPATHI A M, SU W N, HWANG B J. Chem. Soc. Rev., 2018, 47(3):736-851.TRIPATHI A M, SU W N, HWANG B J. Chem. Soc. Rev., 2018, 47(3):736-851.
3. [3]
  LIU Zhen-Bang, MA Ying-Ming, HAN Dong-Xue, DONG Xian-Dui, NIU Li, BAO Yu. Chin. J. Anal. Chem., 2018, 46(8):1171-1177. 刘振邦, 马英明, 韩冬雪, 董献堆, 牛利, 包宇. 分析化学, 2018, 46(8):1171-1177.
4. [4]
  LIAO Yu-Zhi, SI Shi-Hui, CHEN Jin-Hua, LU Yang, DU Ming. Chin. J. Anal. Chem., 2019, 47(7):992-997. 廖玉枝, 司士辉, 陈金华, 卢阳, 杜明. 分析化学, 2019, 47(7):992-997.
5. [5]
  JI Y C, YIN Z W, YANG Z Z, DENG Y P, CHEN H B, LIN C, YANG L Y, YANG K, ZHANG M J, XIAO Q F, LI J T, CHEN Z W, SUN S G, PAN F. Chem. Soc. Rev., 2021, 50(19):10743-10763.JI Y C, YIN Z W, YANG Z Z, DENG Y P, CHEN H B, LIN C, YANG L Y, YANG K, ZHANG M J, XIAO Q F, LI J T, CHEN Z W, SUN S G, PAN F. Chem. Soc. Rev., 2021, 50(19):10743-10763.
6. [6]
  ZHU G J, CHAO D L, XU W L, WU M H, ZHANG H J. ACS Nano, 2021, 15(10):15567-15593.ZHU G J, CHAO D L, XU W L, WU M H, ZHANG H J. ACS Nano, 2021, 15(10):15567-15593.
7. [7]
  WU F X, MAIER J, YU Y. Chem. Soc. Rev., 2020, 49(5):1569-1614.WU F X, MAIER J, YU Y. Chem. Soc. Rev., 2020, 49(5):1569-1614.
8. [8]
  HUANG Su-Qing, HUANG Zhao, GU Tie-An, XIE Qing-Ji, YAO Shou-Zhuo. Chin. J. Anal. Chem., 2011, 39(7):978-984. 黄素清, 黄钊, 谷铁安, 谢青季, 姚守拙. 分析化学, 2011, 39(7):978-984.
9. [9]
  CHAN C K, PATEL R N, O'CONNELL M J. ACS Nano, 2010, 4(3):1443-1450.CHAN C K, PATEL R N, O'CONNELL M J. ACS Nano, 2010, 4(3):1443-1450.
10. [10]
  LIU N, LU Z, ZHAO J, MCDOWELL M T, LEE H W, ZHAO W, CUI Y. Nat. Nanotechnol, 2014, 9(3):187-192.LIU N, LU Z, ZHAO J, MCDOWELL M T, LEE H W, ZHAO W, CUI Y. Nat. Nanotechnol, 2014, 9(3):187-192.
11. [11]
  CHAN C K, PENG H, LIU G, MCILWRATH K, ZHANGX F, HUGGINS R A. Nat. Nanotechnol., 2007, 3(1):31-35.CHAN C K, PENG H, LIU G, MCILWRATH K, ZHANGX F, HUGGINS R A. Nat. Nanotechnol., 2007, 3(1):31-35.
12. [12]
  MAGASINSKI A, ZDYRKO B, KOVALENKO I, HERTZBERG B, BURTOVYY R, HUEBNER C F, FULLER T F, LUZINOV I, YUSHIN G. ACS Appl. Mater. Interfaces, 2010, 2(11):3004-3010.MAGASINSKI A, ZDYRKO B, KOVALENKO I, HERTZBERG B, BURTOVYY R, HUEBNER C F, FULLER T F, LUZINOV I, YUSHIN G. ACS Appl. Mater. Interfaces, 2010, 2(11):3004-3010.
13. [13]
  CHOI S, KWON T W, COSKUN A, CHOI J W. Science, 2017, 357(6348):279-283.CHOI S, KWON T W, COSKUN A, CHOI J W. Science, 2017, 357(6348):279-283.
14. [14]
  RYOU M H, KIM J, LEE I, KIM S, JEONG Y K, HONG S, RYU J H, KIM T S, PARK J K, LEE H, CHOI J W. Adv. Mater., 2013, 25(11):1571-1576.RYOU M H, KIM J, LEE I, KIM S, JEONG Y K, HONG S, RYU J H, KIM T S, PARK J K, LEE H, CHOI J W. Adv. Mater., 2013, 25(11):1571-1576.
15. [15]
  RUFFO R, HONG S S, CHAN C K. J. Phys. Chem. C, 2009, 113(26):11390-11398.RUFFO R, HONG S S, CHAN C K. J. Phys. Chem. C, 2009, 113(26):11390-11398.
16. [16]
  CHANG J B, HUANG X K, ZHOU G H, CUI S M, HALLAC P B, JIANG J W, HURLEY P T, CHEN J H. Adv. Mater., 2014, 26(5):758-764.CHANG J B, HUANG X K, ZHOU G H, CUI S M, HALLAC P B, JIANG J W, HURLEY P T, CHEN J H. Adv. Mater., 2014, 26(5):758-764.
17. [17]
  CHEN H, LING M, HENCZ L, LING H Y, LI G R, LIN Z, LIU G, ZHANG S Q. Chem. Rev., 2018, 118(18):8936-8982.CHEN H, LING M, HENCZ L, LING H Y, LI G R, LIN Z, LIU G, ZHANG S Q. Chem. Rev., 2018, 118(18):8936-8982.
18. [18]
  SONG J X, ZHOU M J, YI R, XU T, GORDIN M L, TANG D H, YU Z X, REGULA M, WANG D H. Adv. Funct. Mater., 2014, 24(37):5904-5910.SONG J X, ZHOU M J, YI R, XU T, GORDIN M L, TANG D H, YU Z X, REGULA M, WANG D H. Adv. Funct. Mater., 2014, 24(37):5904-5910.
19. [19]
  LI Jia-Yu, QI Li, WANG Hong-Yu. Chin. J. Anal. Chem., 2017, 45(4):560-564. 李家玉, 齐力, 王宏宇. 分析化学, 2017, 45(4):560-564.
20. [20]
  PARK C M, KIM J H, KIM H, SOHN H J. Chem. Soc. Rev., 2010, 39(8):3115-3141.PARK C M, KIM J H, KIM H, SOHN H J. Chem. Soc. Rev., 2010, 39(8):3115-3141.
21. [21]
  JIAO X X, YIN J Q, XU X Y, WANG J L, LIU Y Y, XIONG S Z, ZHANG Q L, SONG J X. Adv. Funct. Mater., 2021, 31(3):2005699.JIAO X X, YIN J Q, XU X Y, WANG J L, LIU Y Y, XIONG S Z, ZHANG Q L, SONG J X. Adv. Funct. Mater., 2021, 31(3):2005699.
22. [22]
  LIU D, ZHAO Y, TAN R, TIAN L L, LIU Y, PAN F. Nano Energy, 2017, 36:206-212.LIU D, ZHAO Y, TAN R, TIAN L L, LIU Y, PAN F. Nano Energy, 2017, 36:206-212.
23. [23]
  WANG C, WU H, CHEN Z, MCDOWELL M T, CUI Y, BAO Z A. Nat. Chem., 2013, 5(12):1042-1048.WANG C, WU H, CHEN Z, MCDOWELL M T, CUI Y, BAO Z A. Nat. Chem., 2013, 5(12):1042-1048.
24. [24]
  LIU T C, LIN L P, BI X X, TIAN L L, XU K, PAN F. Nat. Nanotechnol., 2019, 14:50-56.LIU T C, LIN L P, BI X X, TIAN L L, XU K, PAN F. Nat. Nanotechnol., 2019, 14:50-56.
25. [25]
  WANG J, HU Y, ZHAO H, FU H X, PENG K Q. Adv. Mater. Interfaces, 2018, 5(23):1801132.WANG J, HU Y, ZHAO H, FU H X, PENG K Q. Adv. Mater. Interfaces, 2018, 5(23):1801132.
26. [26]
  KOVALENKO I, ZDYRKO B, MAGASINSKI A, HERTZBERG B, MILICEV Z, BURTOVYY R, LUZINOV I, YUSHIN G. Science, 2011, 334(6052):75-79.KOVALENKO I, ZDYRKO B, MAGASINSKI A, HERTZBERG B, MILICEV Z, BURTOVYY R, LUZINOV I, YUSHIN G. Science, 2011, 334(6052):75-79.
27. [27]
  MA X, GAO Y, CHEN M, WU L M. ChemElectroChem, 2017, 4(6):1463-1469.MA X, GAO Y, CHEN M, WU L M. ChemElectroChem, 2017, 4(6):1463-1469.
28. [28]
  LIU W, LIU P, MITLIN D. Adv. Energy Mater., 2020, 10(43):2002297.LIU W, LIU P, MITLIN D. Adv. Energy Mater., 2020, 10(43):2002297.
29. [29]
  ZHAO Q, STALIN S, ARCHER L A. Joule, 2021, 5(5):1119-1142.ZHAO Q, STALIN S, ARCHER L A. Joule, 2021, 5(5):1119-1142.
30. [30]
  WU H, CHAN G, CHOI J W, YANG Y, HU L. Nat. Nanotechnol., 2012, 7(5):310-315.WU H, CHAN G, CHOI J W, YANG Y, HU L. Nat. Nanotechnol., 2012, 7(5):310-315.
31. [31]
  LUO W, CHEN X Q, XIA Y, LI W, YANG J P. Adv. Energy Mater., 2017, 7(24):1701083.LUO W, CHEN X Q, XIA Y, LI W, YANG J P. Adv. Energy Mater., 2017, 7(24):1701083.

扫一扫看文章

计量

PDF下载量: 3
文章访问数: 457
HTML全文浏览量: 113

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

基于原位电化学石英晶体微天平技术的硅基负极粘结剂性能分析

通讯作者: 任晓燕,E-mail:xyren@ciac.ac.cn; 逯乐慧,E-mail:lehuilu@ciac.ac.cn

English

Performance Analysis of Binders for Silicon Anodes by In-situ Electrochemical Quartz Crystal Microbalance Technique

Corresponding author: REN Xiao-Yan, ; LU Le-Hui,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

基于原位电化学石英晶体微天平技术的硅基负极粘结剂性能分析

通讯作者: 任晓燕,E-mail:xyren@ciac.ac.cn; 逯乐慧,E-mail:lehuilu@ciac.ac.cn

English

Performance Analysis of Binders for Silicon Anodes by In-situ Electrochemical Quartz Crystal Microbalance Technique

Corresponding author: REN Xiao-Yan, ; LU Le-Hui,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs